Current Opinion in Colloid & Interface Science 17 (2012) 274–280

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Current Opinion in Colloid & Interface Science

journal homepage: www.elsevier.com/locate/cocis

Progress in microemulsion characterization

Durga P. Acharya ⁎, Patrick G. Hartley 1
CSIRO Division of Materials Science and Engineering, Bayview Avenue, Clayton, VIC 3168, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Microemulsions are technologically important complex fluids. In many applications, they are required to
Received 3 July 2012 accommodate functional additives such as drugs, polymers, and nanoparticles, which increase the complexity
Accepted 5 July 2012 of the systems further. Multiple complementary techniques are required in order to understand and manip-
Available online 14 July 2012
ulate microemulsion behavior. Recent advances in analytical techniques as well as theoretical models have
allowed observation of the nanoscale morphology of different microemulsion forms of increasing complexity
Keywords:
Microemulsions
at ever greater resolution. At the same time, there is increasing interest in the study of dynamic processes
Small-angle scattering within microemulsions using scattering techniques as well as techniques such as fluorescence correlation
NMR spectroscopy and ultrafast IR spectroscopy. This paper reviews these and other recent developments in the
Characterization characterization of microemulsion systems.
Surfactants © 2012 Elsevier Ltd. All rights reserved.
Solubilization

1. Introduction
The term microemulsion first entered the scientific vernacular in
1959, through the work of Jack H. Schulman and others at Columbia
University [1]. They described these systems as ‘optically isotropic,
transparent oil and water dispersions of droplets whose diameters
were ‘somewhat greater than swollen micelles’. Since then the defini-
tion has been refined several times to include key aspects such as the
importance of amphiphiles, the observation that microemulsions are
thermodynamically stable (as distinct from conventional emulsions
and ‘mini- or ‘nano-’ emulsions), that they can exist as bicontinuous
systems, and more recently that their aqueous phase can be replaced
with other polar components such as room temperature ionic liquids.
Nonetheless, the basic properties which Schulman identified have led
to the development of microemulsion systems in important applica-
tions, such as the delivery of food, consumer products and pharma-
ceuticals, as well as in petrochemical recovery [2–4].
Microemulsion science has relied heavily on characterization
techniques, both from the perspective of fundamental elucidation of
phase and nanostructural behavior, as well as through identifying
the unique properties which make them ‘fit for function’ in the appli-
cations mentioned above.
The classical starting point for microemulsion characterization is
the ternary phase diagram shown in Fig. 1. Represented simply, this
involves generating oil, water and surfactant mixtures, and identify-
ing compositions which form a single phase. More complex
⁎ Corresponding author. Tel.: +61 3 9545 2518.
E-mail addresses: Durga.Acharya@csiro.au (D.P. Acharya), Patrick.Hartley@csiro.au
(P.G. Hartley).
1
Tel.: +61 3 9545 2595.
characterization techniques, which are the focus of this review article,
are then employed to reveal the detailed physicochemical properties
of this microemulsion region, and most importantly their variations
as a function of composition and environment. More recently, these
studies have extended to studying compositions of increasing com-
plexity and to elucidate the substructure of the polar and non‐polar
compartments within the system. Dynamic structural rearrangements
within microemulsions due to various stimuli are also a focus of cur-
rent research. Recent developments across the spectrum of techniques
applied to microemulsion characterization are reviewed in this article,
which is intended as an update to an excellent earlier review in this
journal [5].
2. Electron microscopy
Electron microscopy (EM) techniques were instrumental in the
description of microemulsions by Schulman in 1959 [1]. They contin-
ue to develop, and offer the potential for direct visualization of the
microstructure of microemulsions and other lyotropic mesophases
at b 5 nm resolution. Transmission (TEM) and scanning (SEM) tech-
niques have been used to study internal and surface mesophase
nanostructure [6,7]. The general approach to TEM analysis is to pre-
pare a sample as a thin film, such that an electron beam can pass
through it. The image is collected with contrast resulting from differ-
ential absorption and scattering of electrons from different regions of
the sample. As with all EM based techniques, imaging artefacts due to
sample preparation and dehydration are a major consideration. This
has led to the development of cryogenic preparation (cryo-TEM)
and freeze-fracture (FFEM) techniques [8].
The cryo-TEM technique combines cryogenic preparation techniques
with conventional transmission electron microscopy. Here, a thin film

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doi:10.1016/j.cocis.2012.07.002
 D.P. Acharya, P.G. Hartley / Current Opinion in Colloid & Interface Science 17 (2012) 274–280
Fig. 1. Schematic ternary phase diagram of a mixture of water, oil and surfactant.
Oil-in-water (O/W) microemulsion (L1), water-in-oil (W/O) microemulsion (L2) and
bicontinuous microemulsion regions are highlighted. 2ϕ and 3ϕ are two-phase and
three phase regions, respectively. Adapted from ref. [4].
of sample is rapidly vitrified without ice or sample crystallisation, and
structures captured in the film are observed directly in a frozen-
hydrated state, i.e. very close to their native non-dehydrated state. A
recent review article covers experimental technique and applications
of cryo-TEM in the studying different colloidal systems [6].
Cryo-TEM has been commonly used for the characterization of var-
ious mesophases and their colloidal dispersions [6]. Some noticeable
advances have been made in the use of electron microscopy in charac-
terizing microemulsions including the bicontinuous type in recent
years. Cryo-TEM has been used to characterize microemulsions and
other mesophases including sponge phases [9–11]. Bicontinuous
microemulsion phases are seen to have characteristic zig-zag channel-
like complex structures whereas in Water-in-oil/microemulsion sys-
tems, small droplets are seen on a continuous background. A sponge
(L3) phase that forms at very low loading of oil exhibits a bicontinuous
network structure [10].
In freeze fracture TEM (FFTEM), samples are cleaved under vacu-
um. The fracture plane typically follows the interior (hydrophobic)
domains of membrane like structures providing a “face on” view of
samples. It generally produces a clear picture of the network structure
of bicontinuous microemulsions and/or droplets within discontinuous
microemulsion [7,12,13] and therefore can be considered as comple-
mentary to cryo-TEM for the characterization of microemulsions.
Scanning electron microscopy (SEM), another closely related
EM technique, allows the direct mapping of surface features of
microemulsions, but suffers from many of the sample preparation
problems discussed earlier with respect to non-cryogenic TEM tech-
niques, and hence has been less widely applied. Field emission SEM
(FESEM) provides narrower probing beams at low as well as high
electron energy, resulting in both improved spatial resolution and
minimized sample charging and damage. Cryo-FESEM has also been
used to analyse the surface morphological structure of bicontinuous
and discontinuous microemulsions [7,14]. Although the sample prep-
aration in this technique is less invasive than in FF-TEM, since it only
involves the freezing and fracturing of the sample with a knife on the
stage of the microscope, formation of ice crystals during transfer of
the samples often cannot be completely avoided which can make
275
it difficult to distinguish frozen water from microemulsion droplets.
Nevertheless, the technique can be used differentiate bicontinuous
from droplet type microemulsions. Etching of the samples, which
involves increasing temperature to around − 90 °C for a few minutes
to allow surface ice to sublime, and application of an ultra-thin con-
ductive surface coating (e.g. platinum) to prevent charging helps to
minimize interference from frozen water and improve the image
quality, resulting in overall increase in the usefulness of the technique
in characterizing droplet and bicontinuous microemulsions [14].
3. Scattering techniques
Scattering techniques involving X-rays, neutrons and light have
been used to obtain quantitative information on size, shape and mor-
phology of microemulsions. The basic principle of these techniques
involves applying an incident beam of radiation to the sample, and
recording the intensity and angle of the scattered beam. The scattering
arises from the interaction of the radiation with regions of different
refractive index (light scattering), electron density (X-ray scattering)
or nuclear composition (neutron scattering). In the small-angle
x-ray scattering (SAXS) technique, the recorded scattering profile at
low angles is fitted to suitable models to extract information about
the shape, size and nanostructure of scattering elements such as
those found in microemulsions. To reach the scale of interest for
microemulsions (>10 nm) scattering angles smaller than 1° must be
used.
In small-angle neutron scattering (SANS), neutrons from a reactor
source are scattered by the atomic nuclei of the sample. Different
nuclei or even different isotopes of the same element have different
abilities to scatter neutrons, expressed as their characteristic scatter-
ing length density (SLD). There is no systematic variation of SLD with
density or atomic number and it can even be negative. Hence,
through the use of isotopic substitution (e.g. chemical substitution
of hydrogen atoms with deuterium), variable contrasts in neutron
scattering length density can be created within samples to allow a
specific phase of interest to be studied without significant impact on
the physico-chemical properties. An advantage of the use of neutrons
is that neutrons are non-destructive, relative to X-rays, and hence
radiation damage rarely occurs in a neutron based experiment. On
the other hand, the relatively slow data acquisition times and neces-
sity for a powerful neutron source (e.g. nuclear reactor) for neutron
scattering experiments limits their applicability in the study of
dynamic phenomena.
Dynamic light scattering (DLS), also known as photon correlation
spectroscopy, can be used to analyse microemulsion droplet size via
determination of hydrodynamic radius which can be extracted from
measurements of the diffusion constants of diluted dispersed phase
(droplets) undergoing Brownian motion. The technique employs
relatively simple equipment and involves very short experimental
times [15,16].
Application of SAXS in determining shape and size of microemulsion
droplets relies on the difference in the ability of oil and water phases
to scatter x-rays. This property has been commonly used to estimate
the radius of a confined phase in O/W or W/O microemulsions [17,18].
Meanwhile Time resolved SAXS (TR-SAXS) has been used to follow
the change in shape and size of microemulsion droplets to study the
kinetics of phase separation [19].
Recent advances in computational hardware and software have
led to considerable research efforts in developing and refining the
techniques which are used to deconvolute scattering data. Broadly speak-
ing, these can be classified as model-dependent or model-independent
methods. Model-dependent methods consist of fitting experimental
data to scattering functions derived from well defined radial density
profiles for the scattering object. They are particularly useful when the
internal structure of the particle is known from other experimental
techniques or can be predicted. Model-independent approaches such
276 D.P. Acharya, P.G. Hartley / Current Opinion in Colloid & Interface Science 17 (2012) 274–280
as generalized indirect Fourier transformation (GIFT) involve Fourier
transformation of the scattering data to obtain a pair distance distribution
function (PDDF) which is related to form factor and contains information
about shape and size of the particle. The resulting PDDF can be further
deconvoluted to obtain the radial distribution profile of the scattering
particle [20]. Although there is no assumption of the shape of the particle
to obtain its form factor, the derivation of the structure factor, which is a
contribution to the scattering of a particle arising from interparticle inter-
actions, involves an assumption of an appropriate model for interparticle
interactions. Hence, the approach is truly model independent only at low
droplet density where interparticle interaction is negligible. Recently,
Nagao et al. [21] proposed a “relative form factor” method to obtain a
droplet density dependence of the form factor without any assumption
of the profile of structure factor. The method, when applied to reverse
type droplet microemulsions, allowed the form factor and structure
factor to be extracted without any assumption of the structure factor
even in the dense droplet region, although the structure factor obtained
from the method could not be explained by any existing models.
There are various models available for the model dependent anal-
ysis of small angle scattering data from microemulsions. The most
commonly used model for the analysis of scattering data from discon-
tinuous type microemulsion systems is the core-shell model [22]. The
basic form of the model considers a radial density profile varying in a
step-like fashion resulting in a sharp jump at the boundary of concen-
tric domains of different densities (for example, at the hydrophobic
core and hydrophilic shell of O/W microemulsions). A recent paper
[23] discussed the limitations of such a model and proposed an ana-
lytical and continuous density distribution function with a widely
variable shape. It was used to derive an analytical scattering form factor
to describe the scattering from particles with the radial density profile
of homogeneous spheres, shells, or core-shell particles. Analytical
expressions have also been derived for the scattering function from
network junctions, and compared with measured small-angle scatter-
ing data obtained from a nonionic microemulsion system consisting of
cylindrical elements and Y-junctions formed by interconnected cylin-
ders [24]. Recently, scattering functions have been derived for core-
shell structured hard spheres with single as well as multiple (layered)
shells with polydispersity in both core radii and overall diameters.
These models were also tested on a well characterized discontinuous
O/W type microemulsion at various concentrations of oils and surfac-
tant in the system [25].
Scattering data from bicontinuous microemulsions is commonly
analysed by the Teubner–Strey (TS) model which gives two charac-
teristic lengths — repeat distance and correlation length — to describe
the structure [26–28]. Freiberger et al. applied the TS model as well as
the model independent GIFT approach to fit scattering data from
nonionic microemulsion systems undergoing phase transitions from
O/W to W/O type microemulsion via a bicontinuous phase [29]. It
was found that the GIFT approach could be used to fit the scattering
data from both the discontinuous and bicontinuous phases. The pic-
ture of the system based on the form factors and structure factors
extracted from the GIFT approach is interesting. It suggests a gradual
increase in the size of particles, but no significant change in the parti-
cle structure/shape when the system moved from the discontinuous
to the bicontinuous. This is an example of the fact that a good fit to
a model does not guarantee that the model considered provides a cor-
rect description of the system. However, the variation in the extracted
parameters of structure factors was consistent with the expected
structural changes when a normal discontinuous microemulsion trans-
forms to first to bicontinuous then reversed type. As expected, the TS
model on the same system showed good fits to the scattering data for
bicontinuous systems only [29].
Combining SAXS with other techniques allows the correlation of
phase structural information with different microemulsion proper-
ties. For instance, SAXS in combination with near infrared (NIR) spec-
troscopy has been used to characterize the effect of the confinement
of water on its dynamic state in Aerosol OT-hydrocarbon based re-
verse micelles/microemulsions [30]. Here, the SAXS experiment pro-
vided microemulsion drop shape, size and polydispersity while NIR
revealed the hydrogen bonding states of water molecules at different
levels of hydration.
Time resolved-SAXS combined with time resolved turbidity mea-
surement has also been employed to simultaneously monitor the pro-
file of growth of oil droplets and shrinking of microemulsion droplets
as a result of phase separation. Using high flux x-ray beams available
at synchrotron facilities, it is possible to capture scattering patterns at
very short exposure time, typically fractions of a second. This has been
exploited to study the morphological evolution of microemulsion
systems in close to real time [31]. Structural transitions within a poly-
merizing microemulsion containing methacrylate-terminated siloxane
macromonomer as an oil phase were reported recently [31]. The time
evolution of scattering data during the polymerization reaction induced
by x-rays were analyzed by both Teubner–Stery and core-shell models.
The TS model showed that the periodicity of the oil and water domains
decreased and correlation length increased during the polymerization,
indicating shrinkage of the systems in agreement with the results
obtained from the analysis of data by the core-shell model.
Increasingly complex microemulsion mixtures are the subject of
recent SAXS studies. The formation of a transient polymer bridged
droplet network was interpreted from the structure factor extracted
from the SAXS data in a study of the addition of an ABA triblock copol-
ymer to the AOT-water-decane inverse microemulsion system [18].
SANS has been used to characterize both droplet [29,32–34] and
bicontinuous microemulsions [26,27,29,35] with a focus on studying
the evolution of droplet size, and packing at and around the droplet
percolation threshold. Reviews on the applications of SANS to -scCO2,
ionic liquid microemulsions, and microemulsions stabilized by surfac-
tant and copolymer mixtures are available [36].
Neutron spin echo (NSE) spectroscopy, a technique closely related
to SANS, is an excellent tool for measuring the dynamic properties of
microemulsions, such as diffusion of droplets as well as membrane
dynamics and shape fluctuations both in terms of spatial and time
resolution. In this inelastic neutron scattering technique, a polarized
beam of neutrons with a velocity distribution is passed through a
sample placed between two magnetic regions with opposite field
directions. A small change in the velocity of neutrons caused by ex-
change of energy during the scattering process is measured. Analysis
of the inelastic broadening of SANS intensity gives the dynamic struc-
ture factor which is related to detailed real-space dynamics within
the system [37]. A recent review article covers the basic principles,
recent developments, and application of NSE to soft matter [38].
SANS and NSE spectroscopy have been used to study the shape and
structure of microemulsion droplets and their translational diffusion
when a reversed droplet microemulsion system is cooled from room
temperature down to 220 K [39]. The translational and rotational
dynamics of confined water molecules within water droplets have
been studied over more than three decades in time from pico- to
nanoseconds by quasielastic neutron scattering which showed slow
(interfacially bound) and fast (core associated) motions [40]. Such
studies have been extended to reverse microemulsions containing
glycerol as the dispersed phase in investigations of the dynamics of
confined supercooled glycerol [41]. Nagao and Seto [42] analyzed
NSE data from concentrated W/O microemulsion systems by studied
the variation in shape fluctuation and bending elasticity as a function
of the concentration of water (dispersed phase). Wellart et al. [43]
used NSE spectroscopy, in conjunction with dynamic light scattering
technique, to study the influence of temperature variations on the
bending elastic constant of bicontinuous microemulsions formed
by sugar surfactants which show low temperature dependence of
phase behavior. Combination of NSE and DLS techniques, allowed
local thermally excited undulations of the interface to be expressed
in terms of the bending elasticity to be separated from long-range
 D.P. Acharya, P.G. Hartley / Current Opinion in Colloid & Interface Science 17 (2012) 274–280
collective motions, found the undulation of interface independent of
temperature over wide range [43].
Meanwhile, the Dynamic Light scattering (DLS) technique has
been used to characterize discontinuous microemulsions often in
combination with other characterization techniques such as cryo-SEM
[44], SAXS or SANS [18,45,46], turbidimetry [47], nuclear magnetic
resonance spectroscopy [48–50], and absorption and emission spec-
troscopy [51–53]. A recent paper describes a new approach for DLS
data analysis and applies it to a nonionic microemulsion system to ex-
tract information such as free surfactant concentration, micellar molar
composition, surfactant interfacial area and aggregation numbers [16].
4. Nuclear magnetic resonance (NMR)
NMR has been used in the characterization of microemulsions to
study diffusion properties of components and relaxation behavior. A
review article covering the theoretical basis of NMR spectroscopy in
microemulsions is available [54]. Fourier transform pulsed gradient
spin echo (FT-PGSE) technique allows one to measure self-diffusion
coefficients of oil, water and surfactant molecules in the same experi-
ment. In this technique NMR peak attenuation is used to measure the
displacement (translational diffusion) of spins due to specific nuclei in
the lipid/surfactant and water over a defined period in a magnetic field
gradient. Attenuation is measured as a function of field gradient pulse
duration, and the results can be fitted to yield the diffusion coefficient.
The technique permits one to differentiate between discontinuous
and bicontinuous microemulsions and also to determine whether a
discontinuous microemulsion is W/O type or O/W type, since the
oil- or water-continuous phase in discontinuous microemulsions
has a self-diffusion coefficients close to that of the bulk liquid. In
bicontinuous microemulsions, free diffusion of solvent phases is
restricted in two directions due to the presence of the surfactant
stabilised interface, resulting in reduced diffusion coefficients. Hence,
simultaneously high diffusion coefficients of both component solvents
provide evidence of bicontinuous structures, and a sharp change in the
diffusion properties of one of the solvents corresponds to the transition
from bicontinuous to discontinuous microemulsions. The method has
been used, in combination with conductivity and SANS to characterize
gelled polymerizable microemulsions and changes in structure as a
function of temperature [35]. Multinuclear NMR (1H, 31P and 19F) tech-
niques have been used to characterize microemulsions consisting of
water, a fluorinated drug solubilized in oil, and various phospholipid
stabilizers by measuring the diffusion coefficients of the individual com-
ponents [55]. In another application of NMR diffusimetry, the internal
structure of water-in-diesel microemulsions formulated with nonionic
surfactants and with varying amounts of water has been investigated
by determining the diffusion coefficients of diesel hydrocarbons, water
and the surfactants. It was been shown that as the amount of water
increased, the water domains first swell and then multiplied [56]. The
technique is not limited to normal microemulsions but can also be
applied to characterize microemulsions containing ionic liquids [50].
The NMR relaxation technique for characterizing microemulsions
involves measuring the molecular relaxations of component mole-
cules. Using models, it can provide information about aggregate
shape and size, and it is sensitive in picking up subtle changes in
droplet shape and size without any interference from droplet interac-
tions at high volume fractions. The technique has been used obtain in-
formation on water content and the structural organization of reverse
microemulsions formed by AOT surfactants with Mg 2 + and different
alkali metal ions, M + [57]. Free water and water molecules coordinat-
ed with the Mg 2+ ion gave two separate NMR signals, indicating that
the environment in the Mg(AOT)2 microemulsion is different from
microemulsions of MAOT. The technique has also been used to obtain
information on the location and dynamics of a redox fluorophore,
[Ru(bpy)3] 2+ which is used to study the microstructure inside
reverse microemulsions. Combining longitudinal or spin–lattice (T1)
277
relaxation of water molecules, with two-dimensional proton–proton
nuclear Overhauser effect spectroscopy and molecular modelling, it
has been shown that the location of the fluorophore complex depended
on the size of the aqueous core of the microemulsion, with the probe
molecule being located deep inside the surfactant layer for small drop-
let and nearer the interface for larger droplets [48].
5. Spectroscopic techniques
Several spectroscopic techniques have been used to study differ-
ent aspects of microemulsion structures and properties. The absorp-
tion and steady-state emission spectroscopy of probe molecules
solubilized in a microemulsion system can probe the polarity of the
microemulsion at their solvation location [58]. Time-resolved emis-
sion spectroscopy also provides dynamics and rotation relaxation of
solvent in microemulsions [58–60].
Chemiluminescence techniques have also been employed to study
transitions between polar and non-polar environments in microemulsion
systems. For instance, Tetrakis(dimethylamino)ethylene chemilumines-
cence (TDE CL) is based on the transport of quenching species from the
continuous nonpolar phase to the interior polar region of aggregates. It
involves the measurement of emission intensity of TDE CL as a function
of time at various concentrations of surfactant and then fitting the data
to estimate the decay constant which, when plotted against surfactant
concentration, shows a change in trend at the critical micellar concentra-
tion [61]. An advantage of CL analysis over earlier techniques employing
fluorescence probes, is the absence of potentially interfering external
light sources and therefore the possibility of measuring emissions against
a completely dark background. The sensitivity of the emission intensity of
TDE CL to variation in solvent viscosity can also be exploited for measur-
ing the viscosity for reverse microemulsion droplets in solvent (oil).
Fluorescence correlation spectroscopy (FCS), which may be con-
sidered as a miniaturization of DLS, measures the tiny spontaneous
fluctuations in fluorescence intensity of molecules in a very small
volume (spot), and quantifies it by temporarily autocorrelating the
recorded intensity signal to obtain the variation in local concentration
of fluorescent species and hence their diffusion coefficient [62]. The
technique is an excellent tool for measuring molecular diffusion
and size under extremely dilute conditions. In very dilute conditions,
droplets of dispersed particles of reverse microemulsions become
invisible in light scattering experiment due to the so-called optical
matching point condition where the dielectric constant of the dis-
persed phase becomes nearly same as that of the bulk. Another diffi-
culty with the light scattering method applied to microemulsion
system arises from the variation of refractive index of droplets with
increase or decrease in droplet size and consequently the water
content as well as surfactant aggregation number of droplets. In a
polydispersed system, this introduces a refractive index mismatch
among the droplets of different sizes which produces an unusual var-
iation in the droplet size distribution in light scattering measurement
as the system approaches the optical matching point. FCS has been
shown to overcome these difficulties of light scattering and extract
accurate size and polydispersity of reversed microemulsion droplets
using a fluorescent marker [63] and a model that incorporates the
size polydispersity of droplets. A methodology for the correction of
refractive index mismatch and fitting analysis of correlation curves
to extract has also been shown. Although FCS is able to bypass diffi-
culties of light scattering techniques in dilute solutions, its main lim-
itation is that the method is not suitable for bigger particles especially
when the droplet size becomes comparable to or bigger than the size
of the spot the FCS is looking at. Hence the method is complementary
to DLS rather than a substitution.
Fourier transform Infrared (FTIR) spectroscopy has been used to
distinguish between the local environments of water molecules con-
fined in the core of reverse microemulsions because of its high sensi-
tivity to interactions between water molecules in the water pool, and
278 D.P. Acharya, P.G. Hartley / Current Opinion in Colloid & Interface Science 17 (2012) 274–280
between water and surfactant at the interface [64,65]. The technique
has been applied to water-in-scCO2 microemulsions stabilized by a mix-
ture of fluorinated surfactants including fluorinated AOT-analogue
surfactant by studying the stretching and bending bands of water and
the S = O stretching band of the surfactant over wide range of water/
CO2 ratios. The number of water molecules in CO2 as dissolved, associat-
ed with the core, or at the water-surfactant interface as a function of
water content in the system was determined [64]. Performing measure-
ments in the Near Infrared (NIR) region further addressed problems
relating to competing absorption in the mid-IR region [66].
Ultrafast IR spectroscopic techniques have also been employed to
study the hydrogen bonding network and dynamics of water molecules
in reverse micelles/microemulsions [67] or at the interface of AOT
reverse micelles [68]. The technique measures orientational relaxation
of water molecules by exploring the OD stretch of dilute HOD in water
and provides a quantitative determination of the dynamics of water as
a function of size and nature of confining structure.
Dielectric spectroscopy is another spectroscopic technique which
can provide information about the morphology of microemulsions
and dynamics of different polar groups and aggregates by measuring
the variation of conductivity and dielectric constant over a wide range
of frequencies ranging from 10 −5 to 10 9 Hz, or correspondingly
dielectric relaxation processes over a wide range of time from 10 4
to 10 −11 s, due to polarization at the interface between oil and
water phases. The theoretical framework and applications of dielec-
tric spectroscopy in soft material particles have been covered in
review articles [69,70]. Dielectric spectra of the microemulsion sys-
tem can be described by a relaxation function consisting of two par-
tially overlapping but distinguishable relaxation components at high
(above 500 MHz) and low frequency regions which are attributed
to correlated movement of surfactant at the water surfactant inter-
face and combination of slow interfacial relaxation of water and inter-
facial polarization. An additional dielectric relaxation contribution
reported recently has been attributed to additional dielectric polari-
zation mechanics arising from a correlated motion of the anionic
group of the ionized surfactant molecule occurring at the water–sur-
factant interface [71]. Dielectric spectroscopy proves to be a powerful
technique in the study of the structural changes such as organization
and rearrangements of droplets forming clusters when microemulsions
undergo percolation in reverse microemulsions [71,72] as well as in
ionic liquid microemulsions [73].
6. Rheology
The rheological properties of microemulsions depend on the type,
shape and number density of aggregates present, as well as the inter-
actions between these aggregates. Hence, microstructural changes
such as sphere-rod or discontinuous to bicontinuous transitions are
reflected in microemulsion rheology. Bicontinuous microemulsions
exhibit a Newtonian behavior (constant viscosity) at low to medium
shear rates but shear thinning is observed at high shear rates, proba-
bly due to fragmentation of the bicontinuous structure. Discontinuous
microemulsions on the other hand show Newtonian behavior over
a wider range of shear rates [74]. However, differentiation of the types
of microemulsions or identification of the structure of the microemulsion
cannot be done purely on the basis of rheological data, because this mac-
roscopic property is not sensitive enough to detect subtle microstructural
changes such as the transformation of microemulsion to a wormlike
micellar phase induced by temperature [75]. Hence, rheometry has
most often been used in combination with other techniques in the char-
acterization of microemulsions. For example, it has been used in conjunc-
tion with SANS and a phase study to measure the percolation threshold
and nanostructure of microemulsions containing a telechelic polymer
and silica nanoparticles [76,77].
Rheological studies of polymeric bicontinuous microemulsions
(which contain continuously interpenetrating domains of two
immiscible homopolymers stabilized by a copolymer lying at the inter-
face) reveal rich rheological behavior, with Newtonian behavior at low
shear rates and shear thinning under moderate shear [78]. At higher
shear rate, the system showed shear induced bulk phase separation
with the two homopolymer-rich phases being ejected, with the sample
resembling a blend of immiscible polymers under very high shear [78].
It was found that the shear-induced macroscopic phase separation is a
characteristic feature of polymeric microemulsions irrespective of the
viscosity contrast between homopolymer phases.
7. Conductivity
Electrical conductivity remains a simple and inexpensive technique
for microemulsion characterization. It primarily reveals whether an
aqueous or oil phase or both phases are continuous. The conductivity
measurement technique has been used to determine the type of
microemulsion, and to estimate phase boundaries resulting from
changes in composition or temperature [9,35,79]. In combination with
other characterization technique, conductivity has also been used in
microemulsions containing ionic liquids [44,50,52] in which the ionic
liquid replaces the high conductivity aqueous phase in conventional
microemulsions.
8. Ionic liquid microemulsions
Nonaqueous microemulsions consisting of room temperature ionic
liquids (RTILs) as the polar phase have drawn considerable interest in
recent years. A recent review article provides further information on
ionic liquid based microemulsions [80]. RTIL microemulsions exhibit
many similarities with aqueous base microemulsions, such as droplet
and bicontinuous structures. Many characterization techniques used
for aqueous microemulsions are also applicable to RTIL microemulsions.
Micellar aggregates and microemulsions containing alkane, non-
ionic polyoxyethylene alkyl ether surfactant and ethylammonium
ammonium nitrate (EAN) or propylammonium nitrate (PAN) as
polar phase have been characterized by SANS and SAXS [81–83].
SAXS analysis along a line of dilution from oil-rich to RTIL-rich
conditions at a fixed concentration of nonionic surfactant within a
single phase microemulsion domain in the ternary phase diagram
has been used to propose a microstructural change with increase
in IL content [84].
The effect of adding water to an IL-in-oil microemulsion has been
investigated by using DLS, FTIR, 1H NMR, 2D-rotational Overhauser
effect spectroscopy, ITC and conductivity measurement technique.
Added water does not penetrate the surfactant layer but remains
hydrogen bonded to the peripheral second and third oxyethylene
units of surfactant Triton X-100 of the microemulsion droplets in
the vicinity of polar head groups, and results in a transition of large
elliptical droplets into small-sized spherical structures and subse-
quent increase in the number of droplets [85]. Steady state and time
resolved emission spectroscopy using coumarin as probes has been
used to study the effect of added water on solvent and rotational
relaxation dynamics in water-in-RTIL microemulsion [50,86]. With
increase in water content of the microemulsions, the probe molecules
are gradually shifted to the aqueous core and experience free water-
like environment. On the other hand, addition of an ionic liquid to aque-
ous microemulsion system also tunes the curvature of microemulsion.
Here, the ionic liquid behaves like an electrolyte but more effectively,
promoting ultralow interfacial tension, induces a Winsor I → Winsor
III → Winsor II transition [87].
9. Summary
Microemulsions are complex liquids with various structures and
physico-chemical behaviors. Technological application of these systems
often requires additional components such as drugs, polymers, and
 D.P. Acharya, P.G. Hartley / Current Opinion in Colloid & Interface Science 17 (2012) 274–280
nanoparticles which increases the complexity of the systems further.
Multiple complementary techniques are required in microemulsion
characterization. Recent advances in electron microscopy have allowed
observation of the nanoscale morphology of different microemulsion
forms. However, there is ample room to improve, especially in improved
sample preparation and in reducing artefacts such as those arising from
ice formation. Scattering techniques, which are complementary to imag-
ing techniques in the sense that they provide nanostructural informa-
tion in ambient conditions, have been extensively used to characterize
various type of microemulsions based on model dependent and model
independent data analysis. New models have been proposed to refine
droplet structure and accommodate more complex network structures
within bicontinuous systems. However, model choice requires care,
since a good fit to scattering data does not guarantee that the extracted
information is valid. Analysis and model fitting of scattering data con-
tinues to be a developing research field as a result.
Interests in the study of dynamic processes within microemulsions
are increasingly important. Although scattering techniques are excel-
lent in extracting structural information, their main weakness is in the
area of capturing information about dynamic processes at very short
time scales. Neutron spin echo spectroscopy has emerged as a closely
related but complementary technique to SANS because of its ability to
catch information on the dynamics of microemulsion droplets such as
interfacial fluctuation and translational movement.
Ultrafast IR spectroscopy, chemiluminescence and fluorescence
correlation spectroscopy (FCS) are emerging techniques in the area
of microemulsion characterization. The ability of FCS to see the dy-
namics of molecules at very small sample volume and low concen-
tration has made it attractive for the characterization of dilute
solutions. On the other hand techniques like NMR diffusimetry and
relaxation techniques, DLS, and conductimetry are commonly used
to characterize microemulsions due to the availability of equipment
and ease of data analysis. They continue to be widely applied to
classical and novel microemulsions containing ionic liquids and
polymers.
References
[1] Schulman JH, Stoeckenius W, Prince LM. Mechanism of formation and structure of
micro emulsions by electron microscopy. J Phys Chem 1959;63:1677-80.
[2] Gupta S, Moulik SP. Biocompatible microemulsions and their prospective uses in
drug delivery. J Pharm Sci 2008;97:22-45.
[3] Gupta S. Biocompatible microemulsion systems for drug encapsulation and delivery.
Curr Sci 2011;101:174-88.
[4] Paul BK, Moulik SP. Uses and applications of microemulsions. Curr Sci 2001;80:
990–1001.
[5] Gradzielski M. Recent developments in the characterisation of microemulsions.
Curr Opin Colloid Interface Sci 2008;13:263-9.
[6] Kuntsche J, Horst JC, Bunjes H. Cryogenic transmission electron microscopy
(cryo-TEM) for studying the morphology of colloidal drug delivery systems. Int J
Pharm 2011;417:120-37.
[7] Krauel K, Girvan L, Hook S, Rades T. Characterisation of colloidal drug delivery systems
from the naked eye to Cryo-FESEM. Micron 2007;38:796-803.
[8] Belkoura L, Stubenrauch C, Strey R. Freeze fracture direct imaging: a new freeze
fracture method for specimen preparation in cryo-transmission electron micros-
copy. Langmuir 2004;20:4391-9.
[9] Lutz R, Aserin A, Wachtel EJ, Ben-Shoshan E, Danino D, Garti N. A study of the
emulsified microemulsion by SAXS, Cryo-TEM, SD-NMR, and electrical conductivity.
J Dispers Sci Technol 2007;28:1149-57.
[10] Wolf L, Hoffmann H, Talmon Y, Teshigawara T, Watanabe K. Cryo-TEM imaging of
a novel microemulsion system of silicone oil with an anionic/nonionic surfactant
mixture. Soft Matter 2010;6:5367-74.
[11] Margulis-Goshen K, Kesselman E, Danino D, Magdassi S. Formation of celecoxib
nanoparticles from volatile microemulsions. Int J Pharm 2010;393:230-7.
[12] Zhao XY, Xu J, Zheng LQ, Li XW. Preparation of temperature-sensitive microemulsion-
based gels formed from a triblock copolymer. Colloids Surf A Physicochem Eng Asp
2007;307:100-7.
[13] Sharma SC, Tsuchiya K, Sakai K, Sakai H, Abe M, Komura S, et al. Formation
and characterization of microemulsions containing polymeric silicone. Langmuir
2008;24:7658-62.
[14] Lutter S, Koetz J, Tiersch B, Kosmella S. Polymer-modified bicontinuous
microemulsions used as a template for the formation of nanorods. J Dispers Sci
Technol 2009;30:745-52.
279
[15] Silva EJ, Zaniquelli MED, Loh W. Light-scattering investigation on microemulsion
formation in mixtures of diesel oil (or hydrocarbons) plus ethanol plus additives.
Energy Fuel 2007;21:222-6.
[16] Lemyre JL, Lamarre S, Beaupre A, Ritcey AM. A new approach for the characterization
of reverse micellar systems by dynamic light scattering. Langmuir 2010;26:10524-31.
[17] Deen GR, Pedersen JS. Phase behavior and microstructure of C12E5 nonionic
microemulsions with chlorinated oils. Langmuir 2008;24:3111-7.
[18] Blochowicz T, Gogelein C, Spehr T, Muller M, Stuhn B. Polymer-induced transient
networks in water-in-oil microemulsions studied by small-angle x-ray and
dynamic light scattering. Phys Rev E 2007;76.
[19] Deen GR, Oliveira CLP, Pedersen JS. Phase behavior and kinetics of phase separa-
tion of a nonionic microemulsion of C(12)E(5)/water/1-chlorotetradecane upon
a temperature quench. J Phys Chem B 2009;113:7138-46.
[20] Glatter O. Fourier transformation and deconvolution. In: Lindner P, Zemb Th, editors.
Neutrons, X-rays and light: scattering methods applied to soft condensed matter.
Amsterdam: Elsevier; 2002. p. 103-24. [Chapter 5].
[21] Nagao M, Seto H, Yamada NL. Interaction between droplets in a ternary
microemulsion evaluated by the relative form factor method. Phys Rev E 2007;75.
[22] Zemb T. Scattering by microemulsions. In: Lindner P, Zemb Th, editors. Neutrons,
X-rays and light: scattering methods applied to soft condensed matter. Amsterdam:
Elsevier; 2002. p. 317-50. [Chapter 13].
[23] Foster T. Universal analytical scattering form factor for shell-, core-shell, or homo-
geneous particles with continuously variable density profile shape. J Phys Chem B
2011;115:10207-17.
[24] Foster T, Safran SA, Sottmann T, Strey R. Scattering form factors for self-assembled
network junctions. J Chem Phys 2007;127.
[25] Nayeri M, Zackrisson M, Bergenholtz J. Scattering functions of core-shell-struct
ured hard spheres with Schulz-distributed radii. J Phys Chem B 2009;113:
8296-302.
[26] Dave H, Gao F, Schultz M, Co CC. Phase behavior and SANS investigations of edible
sugar-limonene microemulsions. Colloids Surf A Physicochem Eng Asp 2007;296:
45-50.
[27] Wellert S, Karg M, Imhof H, Steppin A, Altmann HJ, Dolle M, et al. Structure of
biodiesel based bicontinuous microemulsions for environmentally compatible
decontamination: a small angle neutron scattering and freeze fracture electron
microscopy study. J Colloid Interface Sci 2008;325:250-8.
[28] Acosta EJ, Szekeres E, Harwell JH, Grady BP, Sabatini DA. Morphology of ionic
microemulsions: comparison of SANS studies and the net-average curvature
(NAC) model. Soft Matter 2009;5:551-61.
[29] Freiberger N, Moitzi C, de Campo L, Glatter O. An attempt to detect bicontinuity
from SANS data. J Colloid Interface Sci 2007;312:59-67.
[30] Balakrishnan S, Javid N, Weingartner H, Winter R. Small-angle x-ray scattering
and near-infrared vibrational spectroscopy of water confined in aerosol-OT re-
verse micelles. Chemphyschem 2008;9:2794-801.
[31] Peng SH, Guo QP, Hughes TC, Hartley PG. In situ synchrotron SAXS study of
polymerizable microemulsions. Macromolecules 2011;44:3007-15.
[32] Foster T, Sottmann T, Schweins R, Strey R. Small-angle neutron scattering from
giant water-in-oil microemulsion droplets. I. Ternary system. J Chem Phys
2008;128.
[33] Foster T, Sottmann T, Schweins R, Strey R. Small-angle-neutron-scattering from
giant water-in-oil microemulsion droplets. II. Polymer-decorated droplets in a
quaternary system. J Chem Phys 2008;128.
[34] Silva BFB, Marques EF, Olsson U, Linse P. Size, shape, and charge of salt-free
catanionic microemulsion droplets: a small-angle neutron scattering and model-
ing study. J Phys Chem B 2009;113:10230-9.
[35] Stubenrauch C, Tessendorf R, Salvati A, Topgaard D, Sottmann T, Strey R, et al.
Gelled polymerizable microemulsions. 2. Microstructure. Langmuir 2008;24:
8473-82.
[36] Melnichenko YB, Wignall GD. Small-angle neutron scattering in materials science:
recent practical applications. J Appl Phys 2007;102.
[37] Watson MC, Brown FLH. Interpreting membrane scattering experiments at the
mesoscale: the contribution of dissipation within the bilayer. Biophys J 2010;98:
L9–L11.
[38] Farago B. Recent developments and applications of NSE in soft matter. Curr Opin
Colloid Interface Sci 2009;14:391-5.
[39] Spehr T, Frick B, Grillo I, Falus P, Muller M, Stuhn B. Structure and dynamics of
reverse micelles containing supercooled water investigated by neutron scatter-
ing. Phys Rev E 2009;79.
[40] Spehr TL, Frick B, Zamponi M, Stuhn B. Dynamics of water confined to reverse AOT
micelles. Soft Matter 2011;7:5745-55.
[41] Blochowicz T, Gouirand E, Fricke A, Spehr T, Stuhn B, Frick B. Accelerated dynamics
of supercooled glycerol in soft confinement. Chem Phys Lett 2009;475:171-4.
[42] Nagao M, Seto H. Concentration dependence of shape and structure fluctuations
of droplet microemulsions investigated by neutron spin echo spectroscopy. Phys
Rev E 2008;78.
[43] Wellert S, Karg M, Holderer O, Richardt A, Hellweg T. Temperature dependence of the
surfactant film bending elasticity in a bicontinuous sugar surfactant based
microemulsion: a quasielastic scattering study. Phys Chem Chem Phys 2011;13:3092-9.
[44] Rabe C, Koetz J. CTAB-based microemulsions with ionic liquids. Colloids Surf A
Physicochem Eng Asp 2010;354:261-7.
[45] Causse J, Oberdisse J, Jestin J, Lagerge S. Small-angle neutron scattering study of
solubilization of tributyl phosphate in aqueous solutions of L64 pluronic triblock
copolymers. Langmuir 2010;26:15745-53.
[46] Debbabi K, Guittard F, Eastoe J, Rogers S, Geribaldi S. Reverse water-in-
fluorocarbon microemulsions stabilized by new polyhydroxylated nonionic fluo-
rinated surfactants. Langmuir 2009;25:8919-26.
280 D.P. Acharya, P.G. Hartley / Current Opinion in Colloid & Interface Science 17 (2012) 274–280
[47] Deen GR, Pedersen JS. Nucleation of an oil phase in a nonionic microemulsion-
containing chlorinated oil upon systematic temperature quench. J Phys Chem B
2010;114:7769-76.
[48] Binks DA, Spencer N, Wilkie J, Britton MM. Magnetic resonance studies of a redox probe
in a reverse sodium bis(2-ethylhexyl)sulfosuccinate/octane/water microemulsion.
J Phys Chem B 2010;114:12558-64.
[49] Sedgwick MA, Trujillo AM, Hendricks N, Levinger NE, Crans DC. Coexisting aggre-
gates in mixed aerosol OT and cholesterol microemulsions. Langmuir 2011;27:
948-54.
[50] Pramanik R, Sarkar S, Ghatak C, Rao VG, Sarkar N. Ionic liquid containing
microemulsions: probe by conductance, dynamic light scattering, diffusion-
ordered spectroscopy nmr measurements, and study of solvent relaxation dynamics.
J Phys Chem B 2011;115:2322-30.
[51] Sagisaka M, Hino M, Oasa J, Yamamoto M, Yoda S, Takebayashi Y, et al. Character-
ization of water/supercritical CO(2) microemulsion by UV-visible spectroscopy
and dynamic light scattering. J Oleo Sci 2009;58:75-83.
[52] Pramanik R, Sarkar S, Ghatak C, Rao VG, Setua P, Sarkar N. Microemulsions with
surfactant TX100, cyclohexane, and an ionic liquid investigated by conductance,
DLS, FTIR measurements, and study of solvent and rotational relaxation within
this microemulsion. J Phys Chem B 2010;114:7579-86.
[53] Sarkar S, Pramanik R, Ghatak C, Rao VG, Sarkar N. Characterization of 1-ethyl-3-
methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim][Tf(2)N])/TX-100/
cyclohexane ternary microemulsion: investigation of photoinduced electron transfer
in this RTIL containing microemulsion. J Chem Phys 2011;134.
[54] Furo I. NMR spectroscopy of micelles and related systems. J Mol Liq 2005;117:
117-37.
[55] Hoeller S, Kahlig H, Valenta C. Multinuclear NMR characterisation and dermal deliv-
ery of fluorinated drugs in soybean-microemulsion systems. J Pharm Sci 2009;98:
2686-95.
[56] Lif A, Nyden M, Holmberg K. Water-in-diesel microemulsions studied by NMR
diffusometry. J Dispers Sci Technol 2009;30:881-91.
[57] Stahla ML, Baruah B, James DM, Johnson MD, Levinger NE, Crans DC. H-1 NMR
studies of aerosol-OT reverse micelles with alkali and magnesium counterions:
preparation and analysis of MAOTs. Langmuir 2008;24:6027-35.
[58] Saha R, Rakshit S, Mitra RK, Pal SK. Microstructure, morphology, and ultrafast
dynamics of a novel edible microemulsion. Langmuir 2012;28:8309-17.
[59] Pramanik R, Sarkar S, Ghatak C, Rao VG, Sarkar N. Solvent and rotational relaxa-
tion study in ionic liquid containing reverse micellar system: a picosecond fluo-
rescence spectroscopy study. Chem Phys Lett 2011;512:217-22.
[60] Seth D, Chakraborty A, Setua P, Sarkar N. Dynamics of solvent and rotational
relaxation of coumarin-153 in room-temperature ionic liquid 1-butyl-3-methyl
imidazolium tetrafluoroborate confined in poly(oxyethylene glycol) ethers
containing micelles. J Phys Chem B 2007;111:4781-7.
[61] Huang CC, Hohn KL. Tetrakis(dimethylamino)ethylene chemiluminescence (TDE
CL) characterization of the CMC and the viscosity of reversed microemulsions.
J Phys Chem B 2010;114:2685-94.
[62] Haustein E, Schwille P. Fluorescence correlation spectroscopy: novel variations of
an established technique. Annu Rev Biophys Biomol Struct 2007;36:151-69.
[63] Pal N, Verma SD, Singh MK, Sen S. Fluorescence correlation spectroscopy: an efficient
tool for measuring size, size-distribution and polydispersity of microemulsion drop-
lets in solution. Anal Chem 2011;83:7736-44.
[64] Takebayashi Y, Mashimo Y, Koike D, Yoda S, Furuya T, Sagisaka M, et al. Fourier trans-
form infrared spectroscopic study of water-in-supercritical CO2 microemulsion as a
function of water content. J Phys Chem B 2008;112:8943-9.
[65] Sagisaka M, Oike DK, Mashimo Y, Yoda S, Takebayashi Y, Furuya T, et al.
Water/supercritical CO(2) microemulsions with mixed surfactant systems. Lang-
muir 2008;24:10116-22.
[66] Takebayashi Y, Sagisaka M, Sue K, Yoda S, Hakuta Y, Furuya T. Near-infrared spec-
troscopic study of a water-in-supercritical CO2 microemulsion as a function of the
water content. J Phys Chem B 2011;115:6111-8.
[67] Pieniazek PA, Lin YS, Chowdhary J, Ladanyi BM, Skinner JL. Vibrational spectroscopy
and dynamics of water confined inside reverse micelles. J Phys Chem B 2009;113:
15017-28.
[68] Fayer MD, Levinger NE. Analysis of water in confined geometries and at interfaces.
In: Yeung ES, Zare RN, editors. Annual Reviews, vol. 3. Annual Review of Analytical
Chemistry; 2010. p. 89–107. [Annual Review of Analytical Chemistry, vol. 3].
[69] Cametti C. Dielectric properties of soft-particles in aqueous solutions. Soft Matter
2011;7:5494-506.
[70] Bonincontro A, Cametti C. Interfacial characterization of mesoscopic particle sus-
pensions by means of radiowave dielectric spectroscopy: a minireview. Colloids
Surf A Physicochem Eng Asp 2004;246:115-20.
[71] Cametti C. Dielectric and conductometric properties of highly heterogeneous col-
loidal systems. Riv Nuovo Cim 2009;32:185-260.
[72] Wipf R, Jaksch S, Stuhn B. Dynamics in water-AOT-n-decane microemulsions with
poly(ethylene glycol) probed by dielectric spectroscopy. Colloid Polym Sci 2010;288:
589-601.
[73] Lian YW, Zhao KS. Dielectric analysis of micelles and microemulsions formed in a
hydrophilic ionic liquid. I. Interaction and percolation. J Phys Chem B 2011;115:
11368-74.
[74] Sharma G, Wilson K, van der Walle CF, Sattar N, Petrie JR, Kumar M.
Microemulsions for oral delivery of insulin: design, development and evaluation
in streptozotocin induced diabetic rats. Eur J Pharm Biopharm 2010;76:159-69.
[75] da Silva GC, de Morais WA, Neto AAD, Dantas TNC, Fonseca JLC. The relationship
between rheology and dynamic light scattering for a xylene/water/ButOH/C12E9
microemulsion. Colloids Surf A Physicochem Eng Asp 2012;397:42-7.
[76] Puech N, Mora S, Testard V, Porte G, Ligoure C, Grillo I, et al. Structure and rheo-
logical properties of model microemulsion networks filled with nanoparticles.
Eur Phys J E 2008;26:13-24.
[77] Puech N, Mora S, Phou T, Porte G, Jestin J, Oberdisse J. Microemulsion nanocomposites:
phase diagram, rheology and structure using a combined small angle neutron scatter-
ing and reverse Monte Carlo approach. Soft Matter 2010;6:5605-14.
[78] Zhou N, Bates FS, Lodge TP, Burghardt WR. Shear flow behavior of a dynamically
symmetric polymeric bicontinuous microemulsion. J Rheol 2007;51:1027-46.
[79] Li XC, He GH, Zheng WJ, Xiao GK. Study on conductivity property and microstruc-
ture of TritonX-100/alkanol/n-heptane/water microemulsion. Colloids Surf A
Physicochem Eng Asp 2010;360:150-8.
[80] Kunz W, Zemb T, Harrar A. Using ionic liquids to formulate microemulsions: cur-
rent state of affairs. Curr Opin Colloid Interface Sci 2012;17:205-11.
[81] Atkin R, Warr GG. Phase behavior and microstructure of microemulsions with a
room-temperature ionic liquid as the polar phase. J Phys Chem B 2007;111:9309-16.
[82] Atkin R, Bobillier SMC, Warr GG. Propylammonium nitrate as a solvent for amphi-
phile self-assembly into micelles, lyotropic liquid crystals, and microemulsions.
J Phys Chem B 2010;114:1350-60.
[83] Araos MU, Warr GG. Structure of nonionic surfactant micelles in the ionic liquid
ethylammonium nitrate. Langmuir 2008;24:9354-60.
[84] Harrar A, Zech O, Hartl R, Bauduin P, Zemb T, Kunz W. [emim][etSO(4)] as the Polar
phase in low-temperature-stable microemulsions. Langmuir 2011;27:1635-42.
[85] Gao Y, Hilfert L, Voigt A, Sundmachert K. Decrease of droplet size of the reverse
microemulsion 1-butyl-3-methylimidazolium tetrafluoroborate/triton X-100/
cyclohexane by addition of water. J Phys Chem B 2008;112:3711-9.
[86] Seth D, Chakraborty A, Setua P, Sarkar N. Interaction of ionic liquid with water with
variation of water content in 1-butyl-3-methyl-imidazolium hexafluorophosphate
([bmim][PF6])/TX-100/water ternary microemulsions monitored by solvent and
rotational relaxation of coumarin 153 and coumarin 490. J Chem Phys 2007;126.
[87] Liu LP, Bauduin P, Zemb T, Eastoe J, Hao JC. Ionic liquid tunes microemulsion
curvature. Langmuir 2009;25:2055-9.